1283877 (1) 玖、發明說明 【發明所屬之技術領域】 本發明係有關，以導電性聚合物做爲固體電解質層之 固體電解質電容器，及其製造方法者。 【先前技術】 固體電解質電容器之基本元件，如圖1所示，一般以 在經蝕刻處理，比表面積大之金屬箔所成的陽極基體（1) 上形成電介質之氧化皮膜層（2)，其外側形成對向電極之 固體半導體層（以下稱爲固體電解質）（4)，然後依所期望， 更形成導電糊狀物等之導電體層（5)，即製作完成；其次 ，如此之元件，單獨或層合，以導線（6，7)連接，全體再 用環氧樹脂（8)等完全密封，成爲電容器（9)之構件，廣泛 使用於電氣製品。 近年來，隨著電氣機器之數位化、個人電腦之高速化 ，更要求小型而大容量之電容器、於高週波領域具低阻抗 之電容器；最近，甚且有使用具電子傳導性之導電性聚合 物做爲固定電解質之提案。 對於固體電解質之形狀，有以電解氧化聚合使導電性 聚合物之生長起點，在鋁箔上銲接形成鋁箔表面整體金屬 的提案（例如，參照特開平4-3 079 1 7號公報）。 又，謀求提高靜電容量或小型化，而將陽極箔之有效 表面積擴大的技術開發，亦熱烈的在進行；有以鋁箔經蝕 刻處理後，將蝕刻層壓下之技術的提案（例如’參照專利 -5- 1283877 (2) 第3 0843 3 0號公報，及特開2002-260968公報）。 更有，要求半導體標準件之小型化、高密度化、暗藏 於基板內的薄型、基板密著型之固體電解質電容器的提案 (例如，參照特開2002-260967號公報）。 【發明內容】 [發明之揭示] 固體電解質電容器，爲使成爲所定容量之電容器，在 由複數個電容器元件層合而成之陽極接頭，以陽極導線連 接；在含有導電性聚合物之導電體層，以陰極導線連接； 更將整體以環氧樹脂等絕緣性樹脂密封，製作成固體電解 質電容器；但是，在固體電解質電容器之陰極部份的導電 性聚合物黏著步驟中，聚合條件如不加以嚴密的控制，導 電性聚合物之厚度會發生不均勻的情況，以致導電性聚合 物出現較薄部份，容易使糊狀物等與電介質氧化皮膜層直 接接觸，致使漏泄電流上升，因而導電性聚合物必須加厚 ;在所定晶片中，可層合之電容器元件的片數，受到元件 厚度之限制，不能使固體電解質電容器晶片的容量增大； 又，導電性聚合物之黏著厚度不均勻時，會使層合之電容 器元件與電容器元件的接觸面積減少，有使等效串聯電阻 (ESR)增大之問題存在。 爲使導電性聚合物之厚度的離散情況減少，必須長時 間的嚴密控制聚合條件，有使生產性顯著下降之問題存在 -6 - 1283877 (3) 因此’本發明爲解決上述各項問題，以提供能縮短形 成精緻聚合體之必要時間、無短路不良之增加情況，元件 形狀之離散情形極少，而且可以安定的製作較薄之電容器 元件；藉此’可使固體電解質電容器晶片內之電容器元件 的層合片數增加，而得以高容量化，更能使等效串聯電阻 之離散減小，的層合型固體電解質電容器，及其製造方法 爲目的。 本發明之工作同仁，有鑑於上述各項問題，經深入探 討，不斷硏究之結果發現，將固體電解質之形狀整理，形 成導電性聚合物後再壓縮之方法有效；如此所得之固體電 解質電容器，確認可提高在電介質皮膜上形成之固體電解 質的密著性，高容量，而且介質損耗（tan ά )、漏泄電流、 不良率均很小。 更確認以複數片上述之特性優越的固體電解質電容器 元件，層合而成之電容器，可以小型化、高容量化。 即是說，本發明爲提供下述之固體電解質電容器，及 其製造方法者。 (1) 以具有在活門作用金屬多孔體基板表面之電介質 皮膜上，設置有含導電性聚合物之固體電解質，且依基板 之厚度方向壓縮的電容器元件爲特徵之固體電解質電容器 〇 (2) 如上述（1)記載之固體電解質電容器，其中具備有 在活門作用金屬多孔體基板表面之電介質皮膜上，設置有 含導電性聚合物之固體電解質，且在依基板之厚度方向壓 -7- 1283877 (4) 縮的固體電解質層上設置陰極層之電容器元件。 (3) 如上述（1)或（2)記載之固體電解質電容器，其中在 活門作用金屬多孔體之電介質皮膜上的含導電性聚合物之 固體電解質，爲以化學聚合或電化學聚合而設置者。 (4) 如上述（1)〜（3)任一項記載之固體電解質電容器， 其中設置有固體電解質之元件的壓縮後厚度爲，最大高度 (Rmax)在 250μιη 以下者。 (5) 如上述（2)記載之固體電解質電容器，其中具備有 在活門作用金屬多孔體基板表面之電介質皮膜上，設置有 含導電性聚合物之固體電解質層，使在依基板之厚度方向 壓縮的導電性聚合物層之厚度均勻化後，於固體電解質層 上設置陰極層的電容器元件。 (6) 如（1)〜（5)任一項記載之固體電解質電容器，其中 包含壓縮前基板之導電性聚合物層的最大厚度爲Hamax、 最小厚度爲Harnin，包含壓縮後基板之導電性聚合物層的 最大厚度爲Hbmax、最小厚度爲Hbmin時’如下式所示之 厚度差的減少率△ Η，爲在5〜95 %之範圍者。 (Hbmax-Hbmin) ΔΗ (%)= 1 一 - X 10 0 (Hainax-Hamin) (7)如上述（1)〜（6)任一項記載之固體電解質電容器’ 其中設置有固體電解質層之基板，整體的壓縮率，爲在 5〜90%者。 -8 - 1283877 (5) (8) 如上述（1)〜（7)任一項記載之固體電 其中固體電解質之導電性聚合物爲’在具有 活門作用金屬基板上，以有機高分子單體之 聚合、或氣相化學氧化聚合而形成者。 (9) 如上述（1)〜（7)任一項記載之固體電 其中固體電解質之導電性聚合物爲’使具有 活門作用金屬基板，藉由在有機高分子單體 氧化劑含有液的交互浸漬作業之重覆操作而 (10) 如上述（1)〜（9)任一項記載之固體電 其中活門作用金屬多孔體基板爲’平板狀或 (1 1)如上述（1)〜（10)任一項記載之固體 ，其中活門作用金屬多孔體爲，選自鋁、鉬 、鎂、及矽之單體金屬、或此等之合金者。 (12) 如上述（1)〜（1 1)任一項記載之固體 ，其中形成導電性聚合物之有機高分子單體 節環之化合物、或具有苯胺骨架之化合物者 (13) 如上述（12)記載之固體電解質電容 雜五節環之化合物爲，具有噻吩骨架、或具 物骨架之化合物者。 (14) 如上述（13)記載之固體電解質電容 噻吩骨架之單體化合物爲，3 -乙基噻吩、3 ，4-二甲基噻吩、3，4-甲二氧基噻吩、或3 噻吩。 (1 5)如上述（1)〜（14)任一項記載之固體 解質電容器， 電介質皮膜之 溶液化學氧化 解質電容器， 電介質皮膜之 之含有液，及 形成者。 解質電容器， 箔狀者。 電解質電容器 、銅、欽、鉻 電解質電容器 爲，含有雜五 〇 器，其中含有 有多環狀硫化 器，其中具有 -己基噻吩、3 丨，4-乙二氧基 電解質電容器 1283877 (6) ，其中導電性聚合物之固體電解質層的一部份爲， 層結構或原纖維結構者。 (16) —種層合型固體電解質電容器，其特徵爲 數片的上述（1)〜（15)任一項記載之電容器元件層合 〇 (17) 一種層合型固體電解質電容器，其特徵爲 在活門作用金屬多孔體基板表面之電介質皮膜上， 氧化劑使有機高分子單體行氧化聚合而得導電性聚 成固體電解質層之基板，複數片層合且在厚度方向 於固體電解質層之外表表面上設置有陰極層的電容 〇 (18) 如上述（17)記載之層合型電解質電容器， 置有固體電解質層之層合基板的整體壓縮率，爲在 者。 (19) 一種固體電解質電容器之製造方法，其特 在具有電介質皮膜之多孔體的活門作用金屬基板表 藉由氧化劑之作用，以形成導電性聚合物之單體含 氧化劑含有液，形成導電性聚合物之固體電解質層 設置有導電性聚合物之基板依厚度方向壓縮，接著 電解質層上設置陰極層。 (2 0)—種固體電解質電容器之製造方法，其特 在具有電介質皮膜之多孔體的活門作用金屬基板表 藉由氧化劑之作用，以形成導電性聚合物之單體含 氧化劑含有液，形成導電性聚合物之固體電解層， 具有板 ，以複 而成者 ，含有 設置以 合物所 壓縮， 器元件 其中設 5 〜90% 徵爲， 面上， 有液及 後，將 在固體 徵爲， 面上， 有液及 將設置 -10- 1283877 (7) 有導電性聚合物之基板，複數片層合後，依厚度方向壓縮 接著在固體電解質層之外表表面上設置陰極層。 (2 1)—種固體電解質電容器之製造方法，其特徵爲， 在具有電介質皮膜之多孔體的活門作用金屬基板表面上， 藉由氧化劑之作用，以形成導電性聚合物之單體含有液及 氧化劑含有液，形成導電性聚合物之固體電解質層，接著 使設置有固體電解質層之基板依厚度方向壓縮後，在固體 電解質層上設置陰極層，接著依陰極層之厚度方向壓縮。 (22) 如上述（19)〜（21)任一項記載之固體電解質電容器 的製造方法，其中設置有固體電解質層之基板整體，以 5〜90%之壓縮率壓縮。 (23) 如上述（19)〜（21)任一項記載之固體電解質電容器 的製造方法，其中包含壓縮前基板之導電性聚合物層的最 大厚度爲Hamax、最小厚度Hamin，包含壓縮後基板之導 電性聚合物層的最大厚度爲Hbmax、最小厚度爲Hbmin時 ，壓縮至如下式所示之厚度差的減少率△ Η，爲在5〜9 5 % 之範圍。 ΔΗ (%)= (Hbmax — Hbmin) X 10 0 1 ----- (Hamax — Hamin) (24)如上述（19)〜（23)任一項記載之固體電解質電容器 的製造方法，其中在將設置有固體電解質層之基板，依厚 度方向壓縮之步驟後，還有再形成之步驟。 -11 - 1283877 (8) (2 5)如上述（19)〜（23)任一項記載之固體電解質電容器 的製造方法，其中在設置有固體電解質層之基板，依厚度 方向壓縮之步驟後，還有加濕熟化之步驟。 (26)如上述（25)記載之固體電解質電容器的製造方法 ，其中加濕熟化步驟爲，在跳火電壓以下之形成電壓下， 20〜95°C、40〜95%相對濕度之條件下進行者。 參照附上之圖面，就本發明之方法說明如下。 本發明使用之基板（1)表面的電介質皮膜（2)通常是以 具有活門作用之金屬多孔質成形體，經形成處理等而形成 〇 形成中使用之形成液、形成電壓等之形成條件係，因 應製造固體電解質電容器必要之容量、耐電壓等，藉由預 備實驗確認之適當値予以設定者；還有，形成處理之際， 爲防止形成液滲入固體電解質電容器之陽極形成部份，更 爲與在後步驟形成之固體電解質（4)(陰極部份）確實的絕緣 ，設置一般之掩蔽罩（3)。 掩蔽罩材料，可以使用一般的耐熱性樹脂，以可溶於 溶劑或膨脹之耐熱性樹脂或其前驅體、無機質微粉與纖維 素系樹脂所成組成物等爲適合，材料沒有任何限制；具例 的有，聚苯基碼（PPS)、聚醚碼（PES)、氰酸酯樹脂、氟樹 脂（四氟乙烯，及四氟乙烯•全氟烷基乙烯基醚共聚物等） 、低分子量聚醯亞胺、及此等之衍生物、及其前驅體等等 ;以低分子量聚醯亞胺、聚醚碼、氟樹脂、及此等之前驅 體，較爲適合。 -12· 1283877 (9) 一般而言，在電介質氧化皮膜上形成導電性聚合物之 技術’可使用以氣相聚合法形成導電性高分子層，與以電 解聚合法形成導電性高分子層之方法（特開平3_621 7號公 報等）、以有機高分子單體黏著於電介質氧化皮膜上後， 在氧化劑溶液中聚合之溶液化學聚合法（特開平1丨_ 2 5 1 i 9 J 號公報等）、藉由轉換裝置，在每隔所定時間改變陽極之 供電點’使導電性高分子層之厚度均勻化的電化學聚合法 (美國專利第6168639號’及第6313979號公報等）；本發明 中’較適合的是，將活門作用金屬多孔體基板，浸漬於氧 化劑溶液中，取出乾燥之，使用包含有使氧化劑溶液濃度 在基板上徐徐升高之步驟的有機高分子單體之溶液化學氧 化聚合’或氣相化學氧化聚合；以溶液化學氧化聚合，最 爲適用。 使用本發明，如後述之實施例所示，將具有電介質氧 化皮膜之鋁箔，例如，浸漬於3，4-乙二氧基噻吩（EDT)之 異丙醇（IPA)溶液，使此等風乾以完全除去異丙醇；浸漬 於約20重量％之氧化劑（過硫酸銨）水溶液，於4(TC左右加 熱10分鐘，或重覆施行本步驟，可得聚（3，4-乙二氧基噻 吩）之聚合物。 以本發明之方法，使形成的導電性聚合物固體電解質 層，成爲原纖維結構、或板層（較薄之層狀）結構，此等結 構廣範圍的持續聚合物鏈間之重覆，容易造成電子跳躍， 而使電導度上升，想必爲有助於提高低阻抗等之特性者。 在溶液化學聚合法中，單體黏著於陽極基板之具有微 -13- 1283877 (10) 細孔的電介質皮膜上，於成爲導電性高分子之摻雜劑的所 得化合物存在下，由於氧化劑與空氣中水份之作用發生氧 化聚合，生成之聚合物組成物，在電介質表面上形成固體 電解質；此時，爲形成良好之聚合物組成物，必須調整單 體含有液及氧化劑含有液之浸漬時間，以控制單體及氧化 劑之黏著量；例如，浸漬時間過長時，聚合反應不能完結 ，所得聚合物組成物，容易成爲低分子量者；又，在未飽 和濃度之氧化劑含有液中，其浸漬時間過長時，經由含乾 燥步驟之前步驟，黏著於金屬箔基板之氧化劑會再溶解， 同時，黏著之單體、生成之聚合物亦將溶出或流出；造成 聚合物之生成緩慢，同時，流出物使氧化劑含有液產生污 染；同時的事情，也會在單體含有液之浸漬時發生。 顯像時，例如，使用低分子量成份之氧化劑含有液， 會出現單體含有液之著色、聚合物之浮遊、黏著形成之固 體電解質重量有減少之傾向、單體含有液之粘度、比重之 變化等情形。 因此，在本發明之方法中，浸漬於單體含有液及氧化 劑含有液之時間，以含有液中之單體成份及氧化劑成份， 黏著於金屬箔基板之電介質表面所需之充分時間的低於1 5 分鐘以上，爲適合；以0.1秒〜10分鐘較佳，以1秒〜7分鐘 更適合。 進而，爲求單體均勻黏著於電介質表面上及聚合物組 成物上，在以單體含有液浸漬後，必須於空氣中放置一定 時間’使溶媒氣化；此條件隨溶媒之種類而改變，大體上 -14- 1283877 (11) 在0 °c以上至溶媒之沸點爲止之溫度下進行；放置時間， 隨溶媒之種類而改變，大體上以5秒至1 5分鐘爲宜，例如 ，爲醇系溶媒，以5分鐘以內爲佳；此放置時間之設立， 能使單體均勻的黏著於電介質表面上，更可以減少下步驟 之浸漬於氧化劑含有液時的污染。 浸漬於單體含有液，及氧化劑含有液後，在一定之溫 度範圍，依所定時間保持於空氣中，單體進行氧化聚合。 聚合溫度，隨單體之種類而異，例如，吡咯以5 t以 下爲佳，噻吩系必須爲30〜6(TC。 聚合時間，依浸漬時之單體的黏著量而定·，黏著量隨 單體及氧化劑含有液之濃度，粘度等而改變，不能一槪的 規定；一般而言，減少一次之黏著量，可以縮短聚合時間 ;又，增加一次之黏著量，則必須加長聚合時間。 在本發明之方法中，一次之聚合時間爲1 0秒〜30分鐘 ，以3〜15分鐘更爲適合。 以本發明之方法，在電介質皮膜上形成之導電性聚合 物層，藉由電子顯微鏡照相，確認成爲板層結構，或原纖 維結構之形狀。 導電性聚合物之板層結構及原纖維結構，由於聚合物 鏈之單向性的提高、及聚合物鏈間之廣泛的重覆，有助於 成爲提高電導度之要因；對聚合體固體電解質之電導度的 提升及低阻抗化等電容器之特性的提高，料必授與相當之 影響。 在本發明之方法中，爲使形成之導電性聚合物組成物 -15- (12) 1283877 ，在厚度上具有對濕度、熱、應力等之耐性，必須控制浸 漬之次數；上述製造步驟，以對一個陽極基體而言，浸漬 次數爲5次以上，較適合的爲8〜3 0次重覆操作，可以輕易 地形成所期望之固體電解質層。 形成使用於固體電解質電容器之固體電解質的步驟爲 ’將在具有活門作用之金屬上形成電介質皮膜的陽極體， 交互浸漬於單體含有液、及氧化劑含有液、乾燥後，重覆 操作，使之黏著，於空氣中進行化學氧化聚合之過程。 大氣中之溫度，隨聚合物組成物之種類、聚合方法等 而改變，不能總括規定，一般而言，以-70 °C〜250 °C之範 圍較爲適宜。 單體含有液之濃度，爲3〜50重量％，以5〜〜35重量％ 較佳，以10〜25重量％最爲適合；氧化劑含有液之濃度， 爲5〜70質量％，以15〜50重量％較爲適合；又，單體含有 液及氧化劑含有液之粘度，爲lOOcp以下，以3〇cp以下較 佳，以0.6〜10cp最爲適合。 使用本發明，以單體含有液及氧化劑含有液交互浸漬 ’可以形成具有層狀結構（板層結構或原纖維結構）之導電 性聚合物的固體電解質；更於此層中，由於聚合物鏈之單 向性的提高，及產生聚合物鏈間之重覆，確定不必進行各 次之洗淨，以最後進行較爲適合；如此，在聚合步驟中沒 有反應’而餘留之過剩的（未反應的）單體，也可在下次之 步驟聚合，其結果，可以形成廣泛而重覆的具有層狀結構 之導電性聚合物所成之固體電解質。 -16- 1283877 (13) 本發明固體電解質之適合的形成步驟之一爲’包含將 形成上述電介質皮膜層的活門作用金屬陽極箔，浸漬於含 氧化劑之含有液（含有液1)的步驟，及浸漬於含單體及摻 雜劑之含有液（含有液2)的步驟者；依此順序，浸漬於上 述含有液1之後，再浸漬於含有液2之步驟（正順序）進行亦 可；又，依逆順序，將上述活門作用金屬陽極箔，浸漬於 上述含有液2之後，再浸漬於含有液1之步驟進行亦可。 或者另外之實施型態，包含將上述陽極箔，浸漬於含 氧化劑及摻雜劑之溶液（含有液3)的步驟，與浸漬於含單 體之溶液（含有液4)的步驟者，亦可，此情形，亦包含依 正順序浸漬於上述含有液3之後，再浸漬於上述含有液4之 步驟進行，或依逆順序，將上述陽極箔浸漬於上述含有液 4之後，再浸漬於上述含有液3之步驟的製造方法亦可；上 述含有液1至含有液4，分別以懸濁狀態使用亦佳；而且， 上述之浸漬步驟以塗佈作業代替亦可。 含有液1至含有液4之溶媒，因應需求使用相同者亦可 ，或者使用相異之溶媒系亦可；又，因應溶媒之種類，含 有液1與含有液2之間，或含有液3與含有液4之間的步驟， 置入另外之乾燥步驟亦可；而且形成固體電解質後，進行 洗淨亦佳。 本發明中可以使用之具有活門作用的金屬，有鋁、鉬 、鈮、鈦、锆、鎂、矽等之單體金屬、或此等之合金；又 ，對型態而言，壓延箔之蝕刻物、微粉熔結體等之多孔質 成形體之型態均可。 -17- (14) 1283877 其次，陽極基板雖可使用此等金屬之多孔質熔結體、 蝕刻等表面處理板（彩帶、箔等包含在內）、線等，但以平 板狀、箔狀者較爲適合；而且，在此金屬多孔體之表面， 形成電介質氧皮膜之方法，可以使用眾所周知的方法；例 如’使用鉅粉末之熔結體時，可以在磷酸水溶液中進行陽 極氧化，於熔結體形成氧化皮膜。 例如，活門作用金屬箔之厚度，隨使用目的之不同而 異，一般使用厚度在40〜300 μιη之箔；爲製造薄型之固體 電解質電容器，例如鋁箔，使用80〜250 μχη者，設置固體 電解質電容器之元件的壓縮後最大高度（Rmax)，以可達 2 5 Ομιη以下爲適合；金屬箔之大小及形狀，亦隨用途而異 ，平板狀元件單位，以寬約1〜50公厘、長約1〜50公厘之矩 形者爲適合，以寬約2〜15公厘、長約2〜25公厘更加適當。 本發明中，形成固體電解質可以使用之水溶液系氧化 劑有，過氧二硫酸及其鈉鹽、鉀鹽、銨鹽、硝酸鈽（IV)， 硝酸鈽（IV)銨，硫酸鐵（III)，硝酸鐵（III)，氯化鐵（III)等 等；又，有機溶劑系之氧化劑有，有機磺酸鐵，例如，十 二烷基苯磺酸鐵（III)，對-甲苯磺酸鐵（ΙΠ)等等；此處所 用之有機溶劑有，r-丁內酯、及丁醇、異丙醇等一價之 醇類等等；還有，氧化劑溶液之濃度，以5〜50質量％爲宜 ，又，氧化劑溶液之溫度，以-15〜60°C爲適合。 本發明中，用以形成固體電解質之導電性聚合物，爲 具有7Γ電子共軛結構之有機高分子單體的聚合物’其聚合 度爲2以上2000以下，以3〜1 000較適合，以5〜200更爲適當 -18- 1283877 (15) ;具體例有，具有噻吩骨架之化合物，具有多環狀硫化物 骨架之化合物，具有吡咯骨架之化合物，具有呋喃骨架之 化合物、具有苯胺骨架之化合物等含有顯示結構重覆單位 之導電性聚合物等等，導電性聚合物不限定於此等化合物 0 具有噻吩骨架之單體化合物有，3 -甲基噻吩、3 -乙基 噻吩、3-丙基噻吩、3-丁基噻吩、3-戊基噻吩、3-己基噻 吩、3-庚基噻吩、3-辛基噻吩、3-壬基噻吩、3-癸基噻吩 、3 -氟噻吩、3 -氯噻吩、3 -溴噻吩、3 -氰基噻吩、3，4 -二 甲基噻吩、3，4·二乙基噻吩、3，4-丁烯基噻吩、3，4-甲 二氧基噻吩、3，4-乙二氧基噻吩等之衍生物；此等化合 物，可以一般市售之化合物，或以眾所周知之方法（例如 ，合成金屬誌，1 986年，15卷，169頁）準備，對此沒有任 何限制。 又，具有多環狀硫化物骨架之單體化合物，具體例有 ，具有1，3 -二氫多環狀硫化物（別名爲，1，3 ·二氫苯并 [c]噻吩）骨架之化合物、具有1，3-二氫萘并[2，3-c]噻吩 骨架之化合物可以使用；更有，具有1，3-二氫蒽[2，3-c] 噻吩骨架之化合物、具有1，3-二氫并四苯[2，3-c]噻吩骨 架之化合物等等；此等可以眾所周知的方法，例如，特開 平8-3 15 6號公報上記載之方法準備。 又，具有1，3 -二氫萘并[1，2-c]噻吩骨架之化合物， 可以使用1，3_二氫菲并[2，3-c]噻吩衍生物；具有1，3-二氫三苯并[2，3-c]噻吩骨架之化合物，可以使用1，3_二 -19- 1283877 (16) 氫苯并[a]蒽[7，8-c]噻吩衍生物等等。 縮合環上任意含有氮或N-氧化物之化合物，可以使用 1，3-二氫噻吩并[3，4-b]喹喔啉、1，3-二氫噻吩并[3，4-b]喹喔啉-4-氧化物、1，3-二氫噻吩并[3，4-b]喹喔啉-4， 9-二氧化物等等；對此等沒有特別之限制。 具有吡咯骨架之化合物有，3 -甲基吡咯、3 -乙基吡咯 、3 -丙基吡咯、3 - 丁基吡咯、3 -戊基吡咯、3 -己基吡咯、 3 -庚基吡咯、3 -辛基吡咯、3 -壬基吡咯、3 -癸基吡咯、3 -氟吡咯、3-氯吡咯、3-溴吡咯、3-氰基吡咯、3，4-二甲基 吡咯、3，4-二乙基吡咯、3，4-丁烯基吡咯、3，4-甲二 氧基吡咯、3，4-乙二氧基吡咯等之衍生物等等；此等化 合物可以市售品或眾所周知的方法準備，本發明對此沒有 特別之限制。 具有呋喃骨架之化合物有，3 -甲基呋喃、3 -乙基呋喃 、3 -丙基呋喃、3 -丁基呋喃、3 -戊基呋喃、3 -己基呋喃、 3 -庚基咲喃、3 -辛基D夫喃、3 -壬基咲喃、3 -癸基D夫喃、3-氟呋喃、3 -氯咲喃、3-溴呋喃、3 -氰基呋喃、3，4 -二甲基 呋喃、3，4 -二乙基咲喃、3，4 -丁嫌基卩夫喃、3，4 -甲二 氧基呋喃、3 ’ 4 -乙二氧基呋喃等之衍生物等等；此等化 合物可以市售品或眾所周知的方法準備，本發明對此沒有 特別之限制。 具有苯胺骨架之化合物有，2-甲基苯胺、2-乙基苯胺 、2 -丙基苯胺、2 -丁基苯胺、2 -戊基苯胺、2 -己基苯胺、 2 -庚基苯胺、2 -辛基苯胺、2 -壬基苯胺、2 -癸基苯胺、2- -20- 1283877 (17) 氟苯胺、2 -氯苯胺、2-溴苯胺、2 -氰基苯胺、2，5 -二甲基 苯胺、2，5-二乙基苯胺、2，3-丁烯基苯胺、2，3-甲二氧 基苯胺、2，3-乙二氧基苯胺等之衍生物等等；此等化合 物可以市售品或眾所周知的方法準備，本發明對此沒有特 別之限制。 此等之中，以具有噻吩骨架或具有多環狀硫化物骨架 之化合物，較爲適合；以3，4-乙二氧基噻吩（EDT)、1， 3-二氫異硫茚特別適用。 又，上述有機高分子單體之溶媒，以一價醇類（甲醇 、乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第三級丁醇 等）較適合使用；單體溶液中之單體濃度，沒有特別之限 制’可以任意濃度使用。 上述選自化合物群之化合物的聚合條件等，沒有特別 的限制，以簡單的實驗預先確認適合之條件，可以容易的 施行。 又，倂用選自上述單體化合物群之化合物，形成共聚 物之固體電解質亦佳；此時聚合性單量體之組成比等，爲 依賴聚合條件者，適合之組成比、聚合條件，可用簡單的 實驗確認。 例如，EDT單體及氧化劑在適合之溶液型態，前後分 別或一起塗佈於金屬箔之氧化皮膜層，而形成之方法等可 以利用（專利第3040 1 1 3號公報、美國專利第6229689號公報 本發明中適合使用之3，心乙二氧基噻吩（EDT)，溶解 -21 - 1283877 (18) 於上述之一價醇，與水的相容性不佳之故，與高濃度之氧 化劑水溶液接觸時，EDT在其接觸面，良好的進行聚合， 形成原纖維結構或板層結構（薄層狀）之導電性高分子固體 電解質層。 本發明之製造方法中使用的溶液，或固體電解質形成 後之洗淨用溶媒有，例如，四氫呋喃（THF)、二噁烷、二 乙醚等之醚類；丙酮、甲乙酮等之酮類；二甲基甲醯胺、 乙腈、苯甲腈、N-甲基吡咯烷酮（NMP)、二甲基亞碼 (DMSO)等之非質子性極性溶媒；醋酸乙酯、醋酸丁酯等 之酯類；氯仿、氯化甲烯基等之非芳香族性的氯系溶媒； 硝基甲烷、硝基乙烷、硝基苯等之硝基化合物；甲醇、乙 醇、丙醇等之醇類；甲酸、醋酸、丙酸等之有機酸；該有 機酸之酸無水物（例如，無水醋酸等），又水或此等之混合 溶媒，可以使用；較適合的，爲水、醇類、酮類、或此等 之混合系。 本發明之導電性聚合物，使用芳基磺酸系摻雜劑；例 如，摻雜劑之原料可以使用苯磺酸、甲苯磺酸、萘磺酸、 蒽磺酸、蒽醌磺酸等之鹽類。 如此製造而得之固體電解質的電導度，約在0.1〜2 0〇 S/公分之範圍，以約1〜150 S/公分較佳，以約10〜1〇〇 S/公 分之範圍更爲適合。 本發明中，將以氧化聚合在縱（厚度）方向成長而形成 之導電性聚合物組成物層的基板壓縮使用；藉由此壓縮， 如圖2之模式圖所示，使固體電解質層之最大厚度（hl)與 •22- 1283877 (19) 最小厚度（h 2)之差[h 1 - h 2 ]的値變少，同時，基板及導電性 聚合物亦壓縮變薄，形成元件形狀及容量之離散情形極少 ，而且安定之電容器元件。 壓縮，在形成導電性聚合物組成物層之單一電容器元 件基板施行亦可，也可以在電容器元件基板層合之層合型 電容器製造過程，將複數片重疊之最外層施行壓縮。 壓縮，可以將形成導電性聚合物組成物層之基板，以 平板按壓施行；壓縮條件，在不影響電容器特性之範圍內 ，基板本身之壓縮變形也不要緊。 具體的說，壓縮前包含基板之導電性聚合物層的最大 厚度爲Hamax，最小厚度爲Hamin，壓縮後包含基板之導 電性聚合物層的最大厚度爲Hbmax，最小厚度Hbmin時， 如下式所示之厚度差的減少率△ Η，以可達5〜9 5 %之範圍 施行。 ΔΗ (%)= (Hbmax —Hbmin) X 10 0 1 一 --- (Hamax — Hamin) 又，設置有固體電解質層之基板整體（包含單板及層 合板元件之任何一種）的壓縮率，爲5〜9 0 %，以1 〇〜8 5 %較 佳，以15〜80%更爲適合。 電導度爲，在約0.1〜200 S/公分之範圍者，以約丨〜！ 50 s /公分較佳，以約10〜100 S /公分更爲適合。 壓縮之際所使用之成形用平板的材質，沒有特別的規 -23- 1283877 (20) 定，金屬板或具有彈性之材料，例如使用塑膠板，亦可壓 縮；使用具有彈性之平板，在壓縮之際，自然而然之彈性 或塑性變形，使該基板成爲包裹彈性體之形態時，就結果 而言’形成之導電性聚合物組成物層之基板，經壓縮亦可 ;預先將形成導電性聚合物組成物層之基板，複數片層合 ，再經壓縮亦可，重覆壓縮亦佳。 壓縮所需之壓力爲0.05〜2 0 公斤/平方公厘，以 0.1〜10公斤/平方公厘爲較佳，以0.1〜2 公斤/平方公厘 更爲適合；又，壓縮後之元件厚度的最小値有所限制時， 以設定壓縮時之平板的間隔加以限制亦佳。 壓縮時之保持時間爲0.01秒〜5分鐘，以0.1秒〜30秒較 佳，以0.1秒〜10秒更爲適合。 元件在即將壓縮之前，加熱至不滿2 0 0 °C亦佳，或平 板加熱至23 0 °C亦佳，又，雙方均加熱亦佳。 壓縮之際，因應需求，爲防止元件黏著於平板，使用 脫膜劑，例如，水亦佳；或爲防止含導電性聚合物之陰極 層發生溶解或分解等狀態變化，更使用沸點不滿1 00 °C之 有機溶劑亦佳；或在後步驟，使用可去除之界面活性劑亦 佳。 又，在平板上施行電鍍、類金剛石塗佈、特氟隆塗佈 等表面處理，亦可防止元件黏著於平板。 由壓縮產生之電介質皮膜上的缺陷，可在壓縮後之步 驟施行再形成、熟化而修復。 藉由如此之步驟，能使電容器元件之厚度的離散情形 -24 - 1283877 (21) 不再發生，而且可使厚度減薄之故，可提高在所定之電容 器箱櫃容積空間中的基板密度，因而得以突破先前之容量 上限。 更且，電容器元件之薄膜化’單板亦能利用爲電路基 板密著型之電容器。 以本發明之方法，所得覆蓋於陽極體外表面之板層結 構或原纖維結構的固體電解質，相對的產生連續或單獨之 空間；以本發明之方法，所得覆蓋於陽極體外表面之板層 結構或原纖維結構的固體電解質，產生連續或單獨之空間 ;在上述之壓縮步驟中，僅僅使空間之體積變小，而提高 固體電解質之密度，固體電解質之板層結構或原纖維結構 ，依然原封不動的保持著；因此之故，以壓縮使固體電解 質之厚度變薄，對密封步驟等電容器製造之製程中，所承 受之熱應力、機械應力等影響的緩和作用，與壓縮之前沒 有改變；又，不僅是製程，亦包含實際使用電容器之際， 承受來自環境之種種應力，也能對應，可稱爲有效之結構 〇 必須再形成時，可以使用與包含形成電壓等之形成條 件的形成所使用之形成液相同種類的形成液；較適合的， 爲己二酸銨等中性之鹽類，磷酸鹽等亦可使用。 再形成，以在電容器晶片處理前之步驟施行爲佳，在 電容器元件受到損傷時，或受到損傷後，一次施行亦佳。 又，電容器元件或電容器晶片，在大氣中施加電壓， 以加濕熟化亦能修復；預先使電容器元件或電容器晶片在 -25- 1283877 (22) 20°C〜95°C、40%〜95%相對濕度之條件下放置5分鐘〜100小 時後，於常溫〜23 0 °C之大氣中，，施加額定電壓之0.5倍 至不破壞電容器之程度爲止的電壓、或在20 °C〜95 °C、 40%〜95%相對濕度之條件下，施加額定電壓之0.5倍至不破 壞電容器之程度爲止的電壓，亦可修復損傷。 還有，除非壓縮時受到損傷，此等再形成之技巧實際 上沒有必要。 在如此形成的導電性聚合物組成物層之上，爲使與陰 極導線接頭之電接觸良好，以設置導電體層較爲適合，例 如，施行形成導電糊狀物之固體，或電鍍、金屬蒸著之導 電樹脂膜等。 本發明中，亦可以在形成導電體層之後，施行壓縮； 例如，對含有彈性體之導電體層特別有效的，可以藉由壓 縮而塑性變形，更能使其變薄，亦有使導電體層表面平滑 化之效果。 如此所得之固體電解質電容器元件，通常，連接至導 線接頭，例如，將樹脂模具’樹脂提箱、金屬製之外裝提 箱、樹脂浸漬等’施彳了外裝’可做爲各種用途之電容器製 品。 [用以實施發明之最佳型態] 就本發明之代表例’更具體的說明如下’還有’此等 係，爲說明之單一例示’本發明對此沒有任何之限制。 -26- 1283877 (23) 【實施方式】 [實施例1] 將鋁之化成箔（厚度爲100μπι)切取短軸方向3公厘X長 軸方向10公厘，於長軸方向之4公厘與5公厘處劃分隔開， 雙面之週邊塗佈寬1公厘之聚醯亞胺溶液，乾燥後製成掩 蔽罩；此化成箔之3公厘x4公厘的部份，以10重量％之己 二酸銨水溶液，施加4伏特之電壓，在切口部份進行化成 ，形成電介質氧化皮膜；其次，將此鋁箔之3公厘X 4公厘 之部份，以3，4-乙二氧基噻吩溶解，浸漬於1.2莫耳/公升 之異丙醇（IPA)溶液5秒鐘，將此置於室溫下乾燥5分鐘， 浸漬於含有2-蒽醌磺酸鈉0.07重量％之2莫耳/公升的過硫 酸錢水溶液5秒鐘；接著，將此銘范放置於4 0 °C之大氣中 ，進行氧化聚合；進而，使此浸漬步驟及聚合步驟，整體 重覆操作25次，在鋁箔之外表面上形成導電性聚合物之固 體電解質層；將最後生成之聚（3, 4-乙二氧基噻吩），在50 °C之溫水中洗淨，其後於l〇〇°C下進行30分鐘之乾燥，即 形成固體電解質層。 使用膜厚計[皮口克公司製，數位度盤式指示器，DG-205(精確度3μιη)]，將鋁箔緩慢的夾住於膜厚計之測定部 ，測定其厚度；其結果，如圖2之模示圖所示，週邊之鼓 起部份的厚度（hO爲260μιη，中央之蜂腰部份的厚度（h2)爲 210μιη，膜厚之差（hi-h2)爲 50μιη。 其次，將厚度測定後之形成鋁箔的導電性聚合物組成 物層之部份，置於間隙之最小値爲140μηι的金屬模具上， -27- 1283877 (24) 以約1.5公斤/平方公厘之壓力壓縮成形；接著，以同樣 的方法測定膜厚；其結果，如圖2之模式圖所示，最大厚 度（hi)爲180μηι，最小厚度（h2)爲170μιη，膜厚之差（hi-h2)爲 10μπι ;壓縮後之固體電解質層的厚度差之減少率（△ H)爲 80%，壓縮率爲約30%。 其次，將形成電解質層之3公厘X 4公厘的部份，浸漬 於15重量％之己二酸銨溶液中，在未形成固體電解質層部 份之活門作用金屬箔上設置陽極之接點，施加3.8伏特之 電壓，進行再形成。 再其次，如圖3所示，在上述形成鋁箔之導電性聚合 物組成物層的部份，以碳糊狀物及銀糊化物黏著，將上述 鋁箔4片層合，連接於陽極導線接頭；又，在未形成導電 性聚合物組成物層的部份，以焊接連接於陽極導線接頭； 更以環氧樹脂將此元件密封後，在1 2 5 °C下以額定電壓（2 伏特）施加，進行2小時之熟化，即完成合計30個之電容器 〇 對於3 0個之電容器元件，測定其初期特性之1 2 〇 Hz下 的各量與損耗係數[tan δ X 1 〇〇(%)]，等效串聯電阻（ESR) ，及漏泄電流；還有，漏泄電流是在施加額定電壓1分鐘 後測定；表1爲此等之測定値的平均値、與以〇. 〇 〇 2 c v以上 之漏泄電流爲不良品之不良率；此處，漏泄電流之平均値 爲不良品除外之計算値。 [實施例2(1)〜2(3)] -28 - 1283877 (25) 以與實施例1中相同之製造條件，形成固體電解質後 ，經壓縮與層合，施行各種組合。 [實施例2(1)]1283877 (1) Field of the Invention The present invention relates to a solid electrolyte capacitor using a conductive polymer as a solid electrolyte layer, and a method for producing the same. [Prior Art] As shown in Fig. 1, a basic element of a solid electrolytic capacitor is generally formed of an oxide film layer (2) of a dielectric formed on an anode substrate (1) formed by etching and processing a metal foil having a large specific surface area. a solid semiconductor layer (hereinafter referred to as a solid electrolyte) (4) which forms a counter electrode on the outer side, and then, as desired, a conductor layer (5) of a conductive paste or the like is formed, that is, the fabrication is completed; secondly, such a component, alone Or lamination, connected by wires (6, 7), and completely sealed with epoxy resin (8), etc., and becomes a component of capacitor (9), and is widely used in electrical products. In recent years, with the digitization of electrical equipment and the speed of personal computers, smaller and large-capacity capacitors and capacitors with low impedance in the high-frequency field have been required. Recently, conductive polymerization with electronic conductivity has been used. As a proposal to fix the electrolyte. In the shape of the solid electrolyte, there is a proposal to form a growth starting point of the conductive polymer by electrolytic oxidative polymerization, and to weld the aluminum foil to the entire surface of the aluminum foil (see, for example, Japanese Laid-Open Patent Publication No. Hei 4-3 079 1-7). Further, in order to increase the electrostatic capacity or miniaturization, the development of a technique for enlarging the effective surface area of the anode foil is also carried out enthusiastically; there is a proposal to etch the laminate after the aluminum foil is etched (for example, 'refer to the patent -5- 1283877 (2) Bulletin No. 3 0843 3 0 and JP-A-2002-260968). In addition, a proposal has been made to reduce the size and density of a semiconductor standard, and a thin-type, substrate-tight type solid-electrolyte capacitor that is hidden in a substrate (see, for example, JP-A-2002-260967). [Disclosure of the Invention] The solid electrolytic capacitor is a capacitor having a predetermined capacity, and an anode joint formed by laminating a plurality of capacitor elements is connected by an anode wire; and in a conductor layer containing a conductive polymer, The cathode wire is connected; the whole is sealed with an insulating resin such as epoxy resin to form a solid electrolytic capacitor; however, in the conductive polymer adhesion step of the cathode portion of the solid electrolytic capacitor, the polymerization conditions are not strictly Control, the thickness of the conductive polymer may be uneven, so that the conductive polymer has a thinner portion, and the paste and the like are easily in direct contact with the dielectric oxide film layer, so that the leakage current rises, and thus the conductive polymer It must be thickened; in the given wafer, the number of laminated capacitor elements is limited by the thickness of the element, and the capacity of the solid electrolyte capacitor chip cannot be increased. Moreover, when the thickness of the conductive polymer is uneven, The contact area between the laminated capacitor element and the capacitor element is reduced, Equivalent series resistance (ESR) increases the problem exists. In order to reduce the dispersion of the thickness of the conductive polymer, it is necessary to strictly control the polymerization conditions for a long period of time, and there is a problem that the productivity is remarkably lowered. -6 - 1283877 (3) Therefore, the present invention solves the above problems to Providing an increase in the time required to form a fine polymer without an increase in short-circuit defects, the dispersion of the shape of the element is extremely small, and a thin capacitor element can be made stably; thereby making it possible to make a capacitor element in a solid electrolyte capacitor chip A laminated solid electrolyte capacitor having a large number of laminated sheets and a high capacity, and a discrete series resistance can be further reduced, and a method for producing the same. The working colleagues of the present invention, in view of the above problems, have intensively studied and found that the method of finishing the shape of the solid electrolyte to form a conductive polymer and then compressing is effective; the solid electrolytic capacitor thus obtained, It was confirmed that the adhesion of the solid electrolyte formed on the dielectric film was improved, the capacity was high, and the dielectric loss (tan ά ), leakage current, and defective ratio were small. Further, it has been confirmed that a capacitor obtained by laminating a plurality of solid electrolyte capacitor elements having excellent characteristics described above can be reduced in size and increased in capacity. That is, the present invention provides the following solid electrolyte capacitors and methods for producing the same. (1) A solid electrolytic capacitor (2) characterized by a capacitor element having a solid electrolyte containing a conductive polymer and a capacitor element compressed in the thickness direction of the substrate, having a dielectric film on the surface of the metal porous body substrate The solid electrolytic capacitor according to the above (1), which is provided with a solid electrolyte containing a conductive polymer on a dielectric film on the surface of the metal-coated body substrate, and is pressed in the thickness direction of the substrate by -7 - 1283877 ( 4) A capacitor element of the cathode layer is disposed on the reduced solid electrolyte layer. (3) The solid electrolyte capacitor according to the above (1) or (2), wherein the solid electrolyte containing the conductive polymer on the dielectric film of the metal-working body of the shutter is provided by chemical polymerization or electrochemical polymerization. . (4) The solid electrolytic capacitor according to any one of the above (1), wherein the element having the solid electrolyte has a thickness after compression and a maximum height (Rmax) of 250 μm or less. (5) The solid electrolyte capacitor according to the above (2), wherein a dielectric electrolyte film containing a conductive polymer is provided on the dielectric film on the surface of the metal-coated metal substrate, and is compressed in the thickness direction of the substrate. After the thickness of the conductive polymer layer is uniformized, a capacitor element of the cathode layer is provided on the solid electrolyte layer. (6) The solid electrolytic capacitor according to any one of (1) to (5), wherein the conductive polymer layer including the substrate before compression has a maximum thickness of Hamax and a minimum thickness of Harnin, and comprises conductive polymerization of the compressed substrate. When the maximum thickness of the layer is Hbmax and the minimum thickness is Hbmin, the decrease ratio Δ 厚度 of the thickness difference as shown in the following formula is in the range of 5 to 95%. (Hbmax-Hbmin) ΔΗ (%) = 1 - X 10 0 (Hainax-Hamin) (7) A solid electrolytic capacitor according to any one of the above (1) to (6), wherein a substrate in which a solid electrolyte layer is provided The overall compression ratio is between 5 and 90%. -8 - 1283877 (5) (8) The solid electrolyte according to any one of the above (1) to (7) wherein the conductive polymer of the solid electrolyte is 'on a metal substrate having a shutter function, and the organic polymer monomer It is formed by polymerization or gas phase chemical oxidative polymerization. (9) The solid electrolyte according to any one of the above (1) to (7) wherein the conductive polymer of the solid electrolyte is a metal substrate having a gate function, and is interleaved by an organic polymer monomer oxidant-containing liquid. (10) The solid electric device according to any one of the above (1) to (9), wherein the metal porous body substrate is a flat plate or (1 1) as described above (1) to (10) A solid according to any one of the preceding claims, wherein the metal porous body of the working gate is a single metal selected from the group consisting of aluminum, molybdenum, magnesium, and cerium, or an alloy thereof. (12) The solid according to any one of the above (1) to (1), wherein the compound of the organic polymer monomer ring of the conductive polymer or the compound having the aniline skeleton (13) is as described above ( 12) The solid electrolyte capacitor described in the five-membered ring is a compound having a thiophene skeleton or a compound having a skeleton. (14) The solid electrolyte capacitor according to the above (13), wherein the monomer compound of the thiophene skeleton is 3-ethylthiophene, 3,4-dimethylthiophene, 3,4-methyldioxythiophene, or 3 thiophene. (1) The solid solution capacitor according to any one of the above (1) to (14), the solution chemical solute capacitor of the dielectric film, the liquid containing the dielectric film, and the former. Desolvation capacitor, foil. An electrolytic capacitor, a copper, a chrome, a chrome electrolytic capacitor, comprising a heterocyclic sulphur, comprising a polycyclic vulcanizer having a -hexylthiophene, a 3 丨, 4-ethylenedioxy electrolytic capacitor 1283877 (6), wherein A part of the solid electrolyte layer of the conductive polymer is a layer structure or a fibril structure. (16) A laminated laminated solid electrolyte capacitor characterized by a plurality of capacitor element laminates (17) according to any one of the above (1) to (15), characterized in that On the dielectric film on the surface of the metal porous body substrate, the oxidizing agent oxidizes and polymerizes the organic polymer monomer to obtain a substrate which is electrically conductively polymerized into a solid electrolyte layer, and a plurality of sheets are laminated and surface-surface in the thickness direction of the solid electrolyte layer. Capacitor 设置 (18) in which the cathode layer is provided. The laminated electrolyte capacitor according to the above (17), the overall compression ratio of the laminated substrate in which the solid electrolyte layer is provided. (19) A method for producing a solid electrolyte capacitor, which is characterized in that a metal substrate having a porous body of a dielectric film acts as a oxidizing agent to form a monomer-containing oxidizing agent-containing liquid of a conductive polymer to form a conductive polymerization. The substrate in which the solid electrolyte layer is provided with the conductive polymer is compressed in the thickness direction, and then the cathode layer is provided on the electrolyte layer. (20) A method for producing a solid electrolyte capacitor, which is characterized in that a valve body of a porous body having a dielectric film acts as a oxidizing agent to form a monomer containing an oxidizing agent containing a conductive polymer to form a conductive layer. a solid electrolyte layer of a polymer having a plate, which is formed by a composite, containing a composition to be compressed by a compound, wherein the component is set to 5 to 90%, and the surface, after the liquid and after, will be marked as solid. On the surface, there is a liquid and a substrate which is provided with a conductive polymer. -10- 1283877 (7) A substrate having a conductive polymer, after laminating a plurality of sheets, is compressed in the thickness direction and then a cathode layer is provided on the surface of the surface other than the solid electrolyte layer. (2) a method for producing a solid electrolyte capacitor, comprising: forming a monomer-containing liquid of a conductive polymer by an action of an oxidizing agent on a surface of a metal substrate having a porous body having a dielectric film; The oxidant-containing liquid forms a solid electrolyte layer of a conductive polymer, and then the substrate on which the solid electrolyte layer is provided is compressed in the thickness direction, and then a cathode layer is provided on the solid electrolyte layer, followed by compression in the thickness direction of the cathode layer. (22) The method for producing a solid electrolytic capacitor according to any one of the above (19), wherein the entire substrate provided with the solid electrolyte layer is compressed at a compression ratio of 5 to 90%. The method for producing a solid electrolytic capacitor according to any one of the above (19), wherein a maximum thickness of the conductive polymer layer including the substrate before compression is Hamax and a minimum thickness Hamin, and comprises a substrate after compression. When the maximum thickness of the conductive polymer layer is Hbmax and the minimum thickness is Hbmin, the reduction ratio Δ 压缩 of the thickness difference which is compressed to the following formula is in the range of 5 to 95%. Η Η % % % % 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体 固体After the step of compressing the substrate provided with the solid electrolyte layer in the thickness direction, there is a step of reforming. The method for producing a solid electrolytic capacitor according to any one of the above (19), wherein, after the step of compressing the substrate in the thickness direction of the substrate provided with the solid electrolyte layer, There are also steps for humidification and ripening. (26) The method for producing a solid electrolytic capacitor according to the above (25), wherein the humidifying and aging step is carried out under conditions of a forming voltage of at least a flashover voltage of 20 to 95 ° C and a relative humidity of 40 to 95%. By. The method of the present invention will be described below with reference to the attached drawings. The dielectric film (2) on the surface of the substrate (1) used in the present invention is generally a forming condition in which a metal porous body having a shutter function is formed, a forming liquid used for forming a crucible is formed, a voltage is formed, and the like. In order to prevent the formation of a liquid from penetrating into the anode forming portion of the solid electrolytic capacitor, it is necessary to set the necessary capacity and withstand voltage of the solid electrolytic capacitor to be determined by preliminary experiments. The solid electrolyte (4) (cathode portion) formed in the subsequent step is surely insulated, and a general mask (3) is provided. As the masking cover material, a general heat-resistant resin can be used, and a heat-resistant resin or a precursor thereof which is soluble in a solvent or a swelling, a composition of an inorganic fine powder and a cellulose-based resin, and the like can be used, and the material is not limited; Polyphenyl code (PPS), polyether code (PES), cyanate resin, fluororesin (tetrafluoroethylene, and tetrafluoroethylene • perfluoroalkyl vinyl ether copolymer, etc.), low molecular weight polymerization Yttrium, and derivatives thereof, precursors thereof and the like; and low molecular weight polyimine, polyether code, fluororesin, and precursors thereof are suitable. -12· 1283877 (9) In general, a technique for forming a conductive polymer on a dielectric oxide film can be used by forming a conductive polymer layer by a gas phase polymerization method and forming a conductive polymer layer by an electrolytic polymerization method. (Special Chemical Polymerization Method for Polymerization in an Oxidant Solution After Adhesion of an Organic Polymer Monomer to a Dielectric Oxide Film, etc.) (Special Kaiping 1丨_ 2 5 1 i 9 J, etc.) An electrochemical polymerization method in which the thickness of the conductive polymer layer is made uniform by changing the feeding point of the anode at a predetermined time by a conversion device (U.S. Patent Nos. 6,168,639 and 6313979); Preferably, the valve is applied to the porous metal substrate, immersed in the oxidizing agent solution, taken out and dried, and chemically oxidized by using a solution containing an organic polymer monomer having a step of gradually increasing the concentration of the oxidizing agent solution on the substrate. 'Or gas phase chemical oxidative polymerization; chemical oxidative polymerization in solution, most suitable. According to the present invention, an aluminum foil having a dielectric oxide film is immersed in an isopropyl alcohol (IPA) solution of 3,4-ethylenedioxythiophene (EDT), for example, as shown in the examples below. Completely remove the isopropanol; immerse in about 20% by weight of an oxidizing agent (ammonium persulfate) aqueous solution, heat it at 4 (TC for about 10 minutes, or repeat this step to obtain poly(3,4-ethylenedioxythiophene). The polymer of the conductive polymer solid electrolyte layer formed by the method of the present invention has a fibril structure or a plate layer (thin layer) structure, and the structure has a wide range of continuous polymer chains. Repeatedly, it is easy to cause electron jump, and the electrical conductivity is increased, which is presumably to improve the characteristics of low impedance, etc. In the solution chemical polymerization method, the monomer adheres to the anode substrate and has a micro-13-1283877 (10). On the dielectric film of the pores, in the presence of the obtained compound which is a dopant of the conductive polymer, the oxidizing agent is oxidatively polymerized by the action of moisture in the air, and the resulting polymer composition is formed on the surface of the dielectric. a solid electrolyte; at this time, in order to form a good polymer composition, it is necessary to adjust the immersion time of the monomer-containing liquid and the oxidant-containing liquid to control the adhesion of the monomer and the oxidizing agent; for example, when the immersion time is too long, the polymerization reaction cannot be performed. After completion, the obtained polymer composition is likely to be a low molecular weight; and in an oxidant-containing liquid having an unsaturated concentration, when the immersion time is too long, the oxidizing agent adhered to the metal foil substrate is redissolved through the step before the drying step. At the same time, the adhesive monomer and the formed polymer will also be dissolved or flowed out; the formation of the polymer is slow, and at the same time, the effluent causes the oxidant-containing liquid to be contaminated; at the same time, the monomer-containing liquid is impregnated. When developing, for example, using an oxidizing agent-containing solution of a low molecular weight component, there is a tendency for the color of the monomer-containing liquid to be colored, the floating of the polymer, the weight of the solid electrolyte formed by the adhesion, the viscosity of the monomer-containing liquid, and the specific gravity. The change or the like. Therefore, in the method of the present invention, the monomer-containing liquid and the oxidant are immersed. The time required for the liquid to be contained in the liquid containing the monomer component and the oxidant component to be adhered to the surface of the dielectric substrate of the metal foil substrate is less than 15 minutes, which is suitable; 1 second to 10 minutes is better, and 1 second to 7 minutes is more suitable. Further, in order to uniformly adhere the monomer to the surface of the dielectric and the polymer composition, after being immersed in the monomer-containing liquid, it is necessary to allow the solvent to be vaporized in the air for a certain period of time; this condition varies depending on the type of the solvent. In general,-14-1283877 (11) is carried out at a temperature above 0 °c to the boiling point of the solvent; the standing time varies depending on the kind of the solvent, and is preferably from 5 seconds to 15 minutes, for example, alcohol It is preferred that the solvent is within 5 minutes; the setting of the standing time enables the monomer to be uniformly adhered to the surface of the dielectric, and the contamination of the oxidant-containing liquid in the next step can be reduced. After being immersed in the monomer-containing liquid and the oxidizing agent-containing liquid, it is kept in the air for a predetermined period of time in a certain temperature range, and the monomer is oxidatively polymerized. The polymerization temperature varies depending on the type of the monomer. For example, pyrrole is preferably 5 t or less, and thiophene is 30 to 6 (TC. The polymerization time depends on the amount of the monomer adhered during the immersion. The concentration of the monomer and the oxidant contained in the liquid, the viscosity, etc., cannot be changed. Generally, the amount of adhesion can be reduced once, and the polymerization time can be shortened. Further, when the adhesion is increased once, the polymerization time must be lengthened. In the method of the present invention, the polymerization time of one time is from 10 seconds to 30 minutes, and more preferably from 3 to 15 minutes. The conductive polymer layer formed on the dielectric film by the method of the present invention is photographed by an electron microscope. It is confirmed that it is a ply structure or a shape of a fibril structure. The ply structure and fibril structure of the conductive polymer are improved due to the unidirectionality of the polymer chain and the extensive overlap between the polymer chains. It is a factor that contributes to the improvement of electrical conductivity; the improvement of the electrical conductivity of the polymer solid electrolyte and the improvement of the characteristics of the capacitor such as low-impedance are inevitably affected. In order to form the conductive polymer composition -15-(12) 1283877, having resistance to humidity, heat, stress, etc. in thickness, it is necessary to control the number of times of immersion; the above manufacturing steps for one anode substrate The number of times of immersion is 5 or more, and more preferably 8 to 30 times of repeated operations, the desired solid electrolyte layer can be easily formed. The step of forming a solid electrolyte for use in a solid electrolytic capacitor is 'will have a valve function The anode body on which the dielectric film is formed on the metal is immersed in the monomer-containing liquid and the oxidant-containing liquid, dried, and then repeatedly operated to adhere to the process of chemical oxidative polymerization in the air. The type of the polymer composition, the polymerization method, and the like are not particularly limited, and generally, it is preferably in the range of -70 ° C to 250 ° C. The concentration of the monomer-containing liquid is 3 to 50% by weight. Preferably, it is preferably from 5 to 5% by weight, preferably from 10 to 25% by weight; the concentration of the oxidizing agent-containing liquid is from 5 to 70% by mass, more preferably from 15 to 50% by weight; The viscosity of the monomer-containing liquid and the oxidant-containing liquid is preferably less than 100 cp, preferably less than 3 cp, and is 0. 6~10cp is the most suitable. According to the present invention, a solid electrolyte having a layered structure (sheet layer structure or fibril structure) can be formed by alternately impregnating a monomer-containing liquid and an oxidant-containing liquid; more in this layer, due to the polymer chain The improvement of the unidirectionality, and the repetition of the polymer chain, it is determined that it is not necessary to carry out each wash, and it is more suitable to carry out the final process; thus, there is no reaction in the polymerization step and the remaining excess (not The reacted monomer can also be polymerized in the next step, and as a result, a solid electrolyte composed of a broad and repetitive conductive polymer having a layered structure can be formed. -16- 1283877 (13) One of the suitable forming steps of the solid electrolyte of the present invention is a step of immersing a valve-working metal anode foil which forms the dielectric film layer, and immersing it in an oxidizing agent-containing liquid (containing liquid 1), and a step of immersing in a liquid (containing liquid 2) containing a monomer and a dopant; in this order, immersing in the liquid 1 and then immersing in the liquid 2 (positive order) may be performed; In the reverse order, the above-described valve-acting metal anode foil may be immersed in the liquid-containing liquid 2 and then immersed in the liquid-containing liquid 1 to be carried out. Or another embodiment comprising the step of immersing the anode foil in a solution containing the oxidizing agent and the dopant (containing the liquid 3), and the step of immersing in the monomer-containing solution (containing the liquid 4), or In this case, the immersion in the liquid-containing liquid 3 is carried out in the positive order, and the immersion in the liquid-containing liquid 4 is carried out, or the anode foil is immersed in the liquid-containing liquid 4 in the reverse order, and then immersed in the above-mentioned content. The method of producing the liquid 3 may be carried out; and the liquid 1 to the liquid 4 may be used in a suspended state; and the impregnation step may be replaced by a coating operation. The solvent containing liquid 1 to liquid 4 may be used in the same manner as required, or a different solvent system may be used; and depending on the type of solvent, between liquid 1 and liquid 2, or liquid 3 The step of containing the liquid 4 may be carried out in another drying step; and after the solid electrolyte is formed, it is also preferably washed. A metal having a shutter function which can be used in the present invention, a single metal such as aluminum, molybdenum, niobium, titanium, zirconium, magnesium, lanthanum or the like, or an alloy thereof; and, in terms of the type, the calendering of the calendered foil The shape of the porous molded body such as a substance or a fine powder sintered body may be used. -17- (14) 1283877 In the case of the anode substrate, a porous sintered body of such a metal, a surface treatment plate such as etching (including ribbons, foils, etc.), a wire, or the like may be used, but a flat plate or a foil may be used. Further, in the method of forming a dielectric oxygen film on the surface of the porous metal body, a well-known method can be used; for example, when a sintered body of a giant powder is used, anodization can be performed in an aqueous phosphoric acid solution for sintering. The body forms an oxide film. For example, the thickness of the metal foil applied to the shutter varies depending on the purpose of use, and a foil having a thickness of 40 to 300 μm is generally used. For the manufacture of a thin solid electrolytic capacitor such as an aluminum foil, a solid electrolytic capacitor is provided using 80 to 250 μηη. The maximum height (Rmax) of the component after compression is suitable for up to 2 5 Ομηη; the size and shape of the metal foil vary depending on the application, and the flat component unit is about 1 to 50 mm wide and about 10,000 mm long. A rectangular shape of 1 to 50 mm is suitable, and is more suitably about 2 to 15 mm in width and 2 to 25 mm in length. In the present invention, an aqueous solution-forming oxidizing agent which can be used for forming a solid electrolyte is peroxydisulfuric acid and its sodium salt, potassium salt, ammonium salt, cerium (IV) nitrate, ammonium cerium (IV) nitrate, iron (III) sulfate, and nitric acid. Iron (III), iron (III) chloride, etc.; in addition, organic solvent oxidants, organic sulfonic acid iron, for example, iron (III) dodecylbenzenesulfonate, iron p-toluenesulfonate (ΙΠ And the like; the organic solvent used herein is r-butyrolactone, and a monovalent alcohol such as butanol or isopropanol; and the concentration of the oxidizing agent solution is preferably 5 to 50% by mass. Further, the temperature of the oxidizing agent solution is suitably -15 to 60 °C. In the present invention, the conductive polymer for forming a solid electrolyte is a polymer having an organic polymer monomer having a 7-inch electron conjugated structure, and its polymerization degree is 2 or more and 2000 or less, and is preferably 3 to 1,000. 5 to 200 is more suitable -18-1283877 (15); specific examples are compounds having a thiophene skeleton, compounds having a polycyclic sulfide skeleton, compounds having a pyrrole skeleton, compounds having a furan skeleton, and having an aniline skeleton. The compound or the like contains a conductive polymer or the like which exhibits a structural repeat unit, and the conductive polymer is not limited to such a compound 0. A monomer compound having a thiophene skeleton, 3-methylthiophene, 3-ethylthiophene, 3- Propylthiophene, 3-butylthiophene, 3-pentylthiophene, 3-hexylthiophene, 3-heptylthiophene, 3-octylthiophene, 3-mercaptothiophene, 3-mercaptothiophene, 3-fluorothiophene, 3-chlorothiophene, 3-bromothiophene, 3-cyanothiophene, 3,4-dimethylthiophene, 3,4·diethylthiophene, 3,4-butenylthiophene, 3,4-dioxane Derivatives such as thiophene and 3,4-ethylenedioxythiophene; such compounds can be used in general cities The compound sold is prepared by well-known methods (for example, Synthetic Metals, 1986, Vol. 15, pp. 169) without any limitation. Further, a monomer compound having a polycyclic sulfide skeleton, specifically, a compound having a 1,3 - dihydropolycyclic sulfide (alias, 1,3 · dihydrobenzo[c]thiophene) skeleton a compound having a 1,3-dihydronaphtho[2,3-c]thiophene skeleton; more preferably, a compound having a 1,3-dihydroindole [2,3-c]thiophene skeleton, having 1, A compound of 3-dihydrotetracene[2,3-c]thiophene skeleton or the like; these can be prepared by a known method, for example, the method described in JP-A-8-3-15. Further, as the compound having a 1,3 -dihydronaphtho[1,2-c]thiophene skeleton, a 1,3-dihydrophenanthro[2,3-c]thiophene derivative; As the compound of the hydrogen tribenzo[2,3-c]thiophene skeleton, 1,3_di-19-1283877 (16) a hydrogenbenzo[a]indole [7,8-c]thiophene derivative or the like can be used. For the compound containing nitrogen or N-oxide optionally on the condensed ring, 1,3-dihydrothieno[3,4-b]quinoxaline or 1,3-dihydrothieno[3,4-b] can be used. Quinoxaline-4-oxide, 1,3-dihydrothieno[3,4-b]quinoxaline-4,9-dioxide, etc.; and the like is not particularly limited. The compound having a pyrrole skeleton is 3-methylpyrrole, 3-ethylpyrrole, 3-propylpyrrole, 3-butylpyrrole, 3-pentylpyrrole, 3-hexylpyrrole, 3-heptylpyrrole, 3- Octylpyrrole, 3-mercaptopyrrole, 3-mercaptopyrrole, 3-fluoropyrrole, 3-chloropyrrole, 3-bromopyrrole, 3-cyanopyrrole, 3,4-dimethylpyrrole, 3,4- Derivatives such as diethylpyrrole, 3,4-butenylpyrrole, 3,4-methyldioxypyrrole, 3,4-ethanedioxypyrrole, etc.; such compounds are commercially available or well known The method is prepared, and the present invention is not particularly limited thereto. The compound having a furan skeleton is 3-methylfuran, 3-ethylfuran, 3-propylfuran, 3-butylfuran, 3-pentylfuran, 3-hexylfuran, 3-heptylfuran, 3 - octyl D-propran, 3-mercaptopurine, 3-mercapto D-propran, 3-fluorofuran, 3-chloropyran, 3-bromofuran, 3-cyanofuran, 3,4-dimethicone Derivatives such as kifuran, 3,4-diethylfuran, 3,4-butyryrifhen, 3,4-dimethoxyfuran, 3'4-ethylenedioxyfuran, and the like; These compounds can be prepared by a commercially available product or a well-known method, and the present invention is not particularly limited thereto. The compound having an aniline skeleton is 2-methylaniline, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-pentylaniline, 2-hexylaniline, 2-heptylaniline, 2- Octylaniline, 2-nonylaniline, 2-nonylaniline, 2--20-1283877 (17) fluoroaniline, 2-chloroaniline, 2-bromoaniline, 2-cyanoaniline, 2,5-dimethyl Derivatives such as aniline, 2,5-diethylaniline, 2,3-butenylaniline, 2,3-methyldioxyaniline, 2,3-ethanedioxyaniline, etc.; It can be prepared by a commercially available product or a well-known method, and the present invention is not particularly limited thereto. Among these, a compound having a thiophene skeleton or a polycyclic sulfide skeleton is preferred, and 3,4-ethylenedioxythiophene (EDT) or 1,3-dihydroisothiopurine is particularly suitable. Further, the solvent of the above organic polymer monomer is preferably used as a monovalent alcohol (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, etc.); The monomer concentration in the solution is not particularly limited 'can be used at any concentration. The polymerization conditions and the like of the compound selected from the compound group are not particularly limited, and suitable conditions can be easily confirmed in advance by a simple experiment, and can be easily carried out. Further, it is preferable to use a compound selected from the above group of monomer compounds to form a solid electrolyte of the copolymer; in this case, the composition ratio of the polymerizable unitary body is, depending on the polymerization conditions, a suitable composition ratio, polymerization conditions, and the like. Simple experiment confirmation. For example, the EDT monomer and the oxidizing agent are applied to the oxide film layer of the metal foil separately or together in a suitable solution form, and the method of forming the same can be utilized (Patent No. 3040 1 1 3, US Pat. No. 6,229,689) In the present invention, 3 is suitable for use, and ethylenedioxythiophene (EDT) dissolves 21 - 1283877 (18) in the above-mentioned monovalent alcohol, and has poor compatibility with water, and a high concentration of oxidizing agent aqueous solution. At the time of contact, EDT is polymerized well at its contact surface to form a conductive polymer solid electrolyte layer having a fibril structure or a lamellar structure (thin layer). The solution used in the production method of the present invention, or a solid electrolyte is formed. The solvent for the subsequent washing is, for example, an ether such as tetrahydrofuran (THF), dioxane or diethyl ether; a ketone such as acetone or methyl ethyl ketone; dimethylformamide, acetonitrile, benzonitrile or N-methyl. An aprotic polar solvent such as phenylpyrrolidone (NMP) or dimethyl methacrylate (DMSO); an ester such as ethyl acetate or butyl acetate; a non-aromatic chlorine system such as chloroform or methylalkenyl chloride Solvent; nitromethane, a nitro compound such as a ethane group or a nitrobenzene; an alcohol such as methanol, ethanol or propanol; an organic acid such as formic acid, acetic acid or propionic acid; an acid anhydride of the organic acid (for example, anhydrous acetic acid, etc.), Further, water or a mixed solvent of these may be used; more preferably, it is water, an alcohol, a ketone, or a mixed system of the above. The conductive polymer of the present invention uses an arylsulfonic acid-based dopant; For example, the raw material of the dopant may be a salt of benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, sulfonic acid, sulfonic acid, etc. The electrical conductivity of the solid electrolyte thus obtained is about 0. The range of 1 to 2 0 〇 S/cm is preferably about 1 to 150 S/cm, and more preferably about 10 to 1 〇〇 S/cm. In the present invention, a substrate of a conductive polymer composition layer formed by oxidative polymerization in a longitudinal (thickness) direction is used for compression; by this compression, as shown in the schematic diagram of FIG. 2, the solid electrolyte layer is maximized. Thickness (hl) and •22-1283877 (19) The difference between the minimum thickness (h 2) [h 1 - h 2 ] is less, and the substrate and conductive polymer are also compressed and thinned to form the shape and capacity of the element. There are few discrete cases and stable capacitor components. The compression may be performed on a single capacitor element substrate on which the conductive polymer composition layer is formed, or the outermost layer in which the plurality of sheets are overlapped may be compressed in the manufacturing process of the laminated capacitor in which the capacitor element substrate is laminated. By compression, the substrate on which the conductive polymer composition layer is formed can be pressed by a flat plate; under compression conditions, the compression deformation of the substrate itself does not matter within a range that does not affect the characteristics of the capacitor. Specifically, the maximum thickness of the conductive polymer layer including the substrate before compression is Hamax, and the minimum thickness is Hamin. The maximum thickness of the conductive polymer layer including the substrate after compression is Hbmax, and the minimum thickness Hbmin is as shown in the following formula. The reduction ratio Δ 厚度 of the thickness difference is performed in a range of up to 5 to 95%. ΔΗ (%) = (Hbmax - Hbmin) X 10 0 1 - (-Hamax - Hamin) The compression ratio of the entire substrate (including any of the single-plate and laminate elements) provided with the solid electrolyte layer is 5~9 0%, preferably 1 〇~8 5 %, and 15~80% is more suitable. The electrical conductivity is about 0. 1~200 S/cm range, to about 丨~! 50 s / cm is preferred, preferably about 10 to 100 S / cm. The material of the forming plate used for compression is not specified in the specification -23-1283877 (20). The metal plate or the elastic material, for example, the plastic plate, can also be compressed; using the elastic plate, in compression In the case of natural elastic or plastic deformation, when the substrate is in the form of an elastomer, the substrate of the conductive polymer composition layer formed is compressed, and the conductive polymer is formed in advance. The substrate of the composition layer is laminated, and then compressed, and the compression is also good. The pressure required for compression is 0. 05~2 0 kg/平方2, to 0. 1 to 10 kg / cm 2 is preferred, with 0. 1 to 2 kg/cm 2 is more suitable; in addition, when the minimum thickness of the component after compression is limited, it is also preferable to set the interval of the plate during compression. The hold time during compression is 0. 01 seconds ~ 5 minutes, to 0. 1 second to 30 seconds is better, with 0. 1 second to 10 seconds is more suitable. Before the component is compressed, it is better to heat it to less than 200 °C, or the flat plate is heated to 230 °C, and both sides are heated well. At the time of compression, in order to prevent the components from sticking to the flat plate, it is preferable to use a release agent, for example, water, or to prevent the cathode layer containing the conductive polymer from being dissolved or decomposed, and the boiling point is less than 100 Å. The organic solvent of °C is also preferred; or in the latter step, it is also preferred to use a removable surfactant. Further, surface treatment such as plating, diamond-like coating, or Teflon coating is applied to the flat plate to prevent the component from adhering to the flat plate. The defects on the dielectric film produced by the compression can be repaired by re-forming, curing, and the like after the compression. By such a step, the discrete condition of the thickness of the capacitor element -24283877 (21) can no longer occur, and the thickness can be reduced to increase the density of the substrate in the volume space of the capacitor cabinet. Thus, it is possible to break through the previous capacity ceiling. Further, the thinned single layer of the capacitor element can also be utilized as a capacitor of a circuit board type. In the method of the present invention, the resulting solid electrolyte covering the outer layer surface of the anode or the fibril structure is relatively continuous or separate space; in the method of the present invention, the resulting lamellar structure covering the outer surface of the anode or The solid electrolyte of the fibril structure produces a continuous or separate space; in the above-mentioned compression step, only the volume of the space is made smaller, and the density of the solid electrolyte is increased, and the lamellar structure or fibril structure of the solid electrolyte remains intact. Therefore, the thickness of the solid electrolyte is reduced by compression, and the mitigation effect of the thermal stress and mechanical stress on the capacitor manufacturing process such as the sealing step is not changed before the compression; It is not only the process, but also the actual use of the capacitor. It can also be subjected to various stresses from the environment. It can also be called an effective structure. When it is necessary to re-form it, it can be used in the formation of formation conditions including formation voltage and the like. Forming liquid with the same kind of forming liquid; more suitable, is ammonium adipate, etc. The salts, phosphates and the like may also be used. The formation is performed in such a manner as to be performed before the processing of the capacitor wafer, and it is preferably performed once after the capacitor element is damaged or damaged. Moreover, the capacitor element or the capacitor chip is applied with a voltage in the atmosphere, and can be repaired by humidification and aging; the capacitor element or the capacitor chip is previously made at -25 - 1283877 (22) 20 ° C to 95 ° C, 40% to 95%. After standing for 5 minutes to 100 hours under the condition of relative humidity, in the atmosphere at room temperature ~ 23 0 °C, the rated voltage is applied to 0. 5 times the voltage to the extent that the capacitor is not destroyed, or at a temperature of 20 ° C to 95 ° C, 40% to 95% relative humidity, the rated voltage is applied to 0. The voltage can be repaired by 5 times to a voltage that does not damage the capacitor. Also, unless it is damaged during compression, such re-formation techniques are not actually necessary. On the conductive polymer composition layer thus formed, in order to make good electrical contact with the cathode wire tab, it is suitable to provide a conductor layer, for example, to form a solid for forming a conductive paste, or to electroplate or metal to evaporate. A conductive resin film or the like. In the present invention, it is also possible to perform compression after forming the conductor layer; for example, it is particularly effective for the conductor layer containing the elastomer, which can be plastically deformed by compression, can be made thinner, and the surface of the conductor layer can be smoothed. The effect of the transformation. The solid electrolytic capacitor element thus obtained is usually connected to a wire joint. For example, a resin mold 'resin case, a metal case, a resin dipping, etc.' are externally mounted as a capacitor product for various purposes. [Best Mode for Carrying Out the Invention] The present invention is described in more detail with respect to the representative examples of the present invention, and the present invention is not limited in any way. -26- 1283877 (23) [Embodiment] [Example 1] Aluminium was formed into a foil (thickness: 100 μm) and cut into a short axis direction of 3 mm. The long axis direction was 10 mm, and 4 mm in the long axis direction. 5 mm apart, coated with a 1 mm wide polyimine solution on both sides, dried to make a mask; this is 3 mm x 4 mm of the foil, 10% by weight An aqueous solution of ammonium adipate, applying a voltage of 4 volts, is formed in the nick portion to form a dielectric oxide film; secondly, a portion of 3 to 4 mm of the aluminum foil is 3,4-dioxygen The thiophene is dissolved and immersed in 1. 2 m / liter of isopropanol (IPA) solution for 5 seconds, this was dried at room temperature for 5 minutes, immersed in sodium containing 2-sulfonate. 07% by weight of 2 mol/liter of aqueous solution of persulfate for 5 seconds; then, placing the same in the atmosphere at 40 ° C for oxidative polymerization; further, making the impregnation step and the polymerization step as a whole 25 times of coating operation, a solid electrolyte layer of a conductive polymer is formed on the outer surface of the aluminum foil; the finally formed poly(3,4-ethylenedioxythiophene) is washed in warm water at 50 ° C, and thereafter Drying was carried out for 30 minutes at 10 ° C to form a solid electrolyte layer. Using a film thickness meter (manufactured by Pikuk Co., Ltd., digital dial indicator, DG-205 (accuracy 3 μιη)), the aluminum foil was slowly sandwiched between the measurement portions of the film thickness meter, and the thickness thereof was measured. As a result, 2, the thickness of the peripheral portion (hO is 260 μm, the thickness of the central waist portion (h2) is 210 μm, and the difference in film thickness (hi-h2) is 50 μm. The portion of the conductive polymer composition layer forming the aluminum foil after the thickness measurement is placed on a metal mold having a minimum gap of 140 μm, -27 - 1283877 (24) is about 1. 5 kg/mm 2 pressure compression molding; then, the film thickness was measured in the same manner; as a result, as shown in the schematic diagram of Fig. 2, the maximum thickness (hi) was 180 μm, and the minimum thickness (h2) was 170 μm. The difference in thickness (hi-h2) was 10 μm; the reduction ratio (ΔH) of the thickness difference of the solid electrolyte layer after compression was 80%, and the compression ratio was about 30%. Next, a portion of the electrolyte layer of 3 mm X 4 mm is formed, immersed in a 15% by weight ammonium adipic acid solution, and an anode contact is provided on the shutter metal foil on which the solid electrolyte layer portion is not formed. , applied 3. The voltage of 8 volts is reformed. Next, as shown in FIG. 3, the aluminum foil-forming conductive polymer composition layer is adhered to the carbon paste and the silver paste, and the aluminum foil 4 sheets are laminated and connected to the anode lead tab; Further, in the portion where the conductive polymer composition layer is not formed, it is welded to the anode lead joint; after sealing the element with epoxy resin, it is applied at a rated voltage (2 volts) at 1 2 5 °C. After 2 hours of aging, a total of 30 capacitors were completed, and for 30 capacitor elements, the amount and loss coefficient at the initial characteristics of 1 2 〇 Hz were measured [tan δ X 1 〇〇 (%)] , equivalent series resistance (ESR), and leakage current; also, leakage current is measured after applying the rated voltage for 1 minute; Table 1 for the determination of the average 値, 〇. 漏 〇 2 c v or more The leakage current is the defective rate of the defective product; here, the average 値 of the leakage current is the calculation 除外 other than the defective product. [Example 2 (1) to 2 (3)] -28 - 1283877 (25) After forming a solid electrolyte under the same production conditions as in Example 1, various combinations were carried out by compression and lamination. [Embodiment 2 (1)]
除在設置有固體電解質之基板表面，塗佈碳糊狀物與 銀糊狀物後，於依厚度之方向壓縮，所得鋁箔4片層合， 連接於陰極導線接頭以外，其他都和實施例1同樣的裝配 構成。 [實施例2(2)] 除將設置有固體電解質之基板，依厚度方向壓縮，壓 縮之電容器元件4片層合後，依層合之厚度方向再壓縮， 以碳糊狀物與銀糊狀物黏著，連接於陰極導線接頭以外， 其他都和實施例1同樣的裝配構成。Except that the surface of the substrate provided with the solid electrolyte is coated with the carbon paste and the silver paste, and then compressed in the direction of the thickness, the obtained aluminum foil is laminated in four sheets, and is connected to the cathode lead joint, and the other is the same as in the first embodiment. The same assembly. [Example 2 (2)] Except that the substrate provided with the solid electrolyte was compressed in the thickness direction, the compressed capacitor element was laminated, and then recompressed according to the thickness direction of the lamination, with a carbon paste and a silver paste. The object was adhered and connected to the cathode lead joint, and the other assembly was carried out in the same manner as in the first embodiment.
[實施例2(3)] 除將設置有固體電解質之基板，4片層合後，依層合 之厚度方向壓縮，以碳糊狀物與銀糊狀物黏著，連接於陰 極導線接頭以外，其他都和實施例1同樣的裝配構成。 由此等所得之電容器，進行與實施例1同樣的特性評 估，其結果如表1所示。 [實施例3] 實施例1中，除以吡咯替代3，4-乙二氧基噻吩，此時 -29- 1283877 (26) ，於浸漬吡咯溶液後，在3 °C下乾燥5分鐘，更於浸漬氧化 劑溶液後，在5 °C下聚合 1 0分鐘以外，其他都和實施例1 同樣的完成合計30個之電容器。 與實施例1同樣的，測得固體電解質層之最大厚度（h!) 爲290μιη，最小厚度（h2)爲230μιη，膜厚之差（In-lu)爲60μιη ;接著，壓縮後之最大厚度（1^)爲200μιη，最小厚度爲 180μιη，膜厚之差dhO爲20μιη;壓縮後，固體電解質層 之厚度差的減少率（△ Η)爲66.7%。 所得電容器元件，進行與實施例1同樣的特性評估， 其結果如表1所示。 [比較例1] 實施例1中，除使用不經壓縮成形之製作成的電容器 元件以外，其他都和實施例1同樣的完成30個之電容器。 與實施例1同樣的，測得固體電解質層之最大厚度（h!) 爲260μιη，最小厚度爲210μιη，膜厚之差（h^hj爲50μιη。 所得電容器元件，進行與實施例1同樣的特性評估， 其結果如表1所示。 [比較例2 ] 實施例1中，除使用不經壓縮之聚合次數1 5次製作成 的電容器元件以外，其他都和實施例1同樣的完成3 0個之 電容器。 與實施例1同樣的，測得固體電解質層之最大厚度（hi) -30- 1283877 (27) 爲180μιη，最小厚度（h2)爲120μπι，膜厚之差dh2)爲6〇μ 〇 所得電容器元件，進行與實施例1同樣的特彳生評{古 其結果如表1所示。 表1 實施例 初期特性 容量pF 損耗係數 ESR 漏泄電流 不良率 % (等效串聯電阻） μΑ 1 109 0.7 0.007 0.03 0/30 2(1) 108 0.9 0.008 0.06 0/30 2(2) 109 1.6 0.017 0.03 0/30 2(3) 110 1.8 0.018 0.04 0/30 3 105 1.7 0.014 0.09 1/30 比較例1 108* 3.6 0.025 0.05 1/30 比較例2 107 1.9 0.020 0.15 7/30 *未密封（密封時，一部份之元件露出，不能進行正常之密封） 由實施例1〜3及比較例1〜2之結果可知，使壓縮成形之 固體電解質平坦，厚度差（△ Η)儘力減少之固體電解質電 容器，確認具有高容量，低等效串聯電阻（ESR)，而且漏 泄電流，不良率甚小，極爲優越。 [實施例4] -31 - 1283877 (28) 將形成鋁箔之導電性聚合物組成物層的基板’ 2片重 疊後，使形成導電性聚合物組成物層之部份壓縮成形’與 實施例1同樣的測定單板2片層合之元件的固體電解質層之 最大厚度（hi)爲430μιη，最小厚度（h2)爲400μιη，膜厚之差 (hi-h2)爲 30μιη 〇 [實施例5] 除將形成鋁箔之導電性聚合物組成物層的基板，2片 重疊後，使形成導電性聚合物組成物層之部份壓縮成形， 壓縮成形之基板再2片重疊，再壓縮成形以外，其他都和 實施例1同樣的測定單板4片層合之元件的固體電解質層之 最大厚度（In)爲780μιη，最小厚度（h2)爲760μιη，膜厚之差 (hi-h2)爲 20μπι 〇 [產業上利用性] 本發明之固體電解質電容器爲，使用在活門作用金屬 多孔體基板表面之電介質皮膜上，設置有由有機高分子之 導電性聚合物所成固體電解質的基板，依基板之厚度方向 壓縮的電容器元件者；其具有，可以安定的製作形狀之離 散情形極少，而且甚薄的電容器元件，可以建造高度甚低 、小型而高容量之層合型固體電解質電容器，固體電解質 電容器具有無短不良而且安定之性能等的特長。 【圖式簡單說明】 -32- 1283877 (29) 圖1爲，使用電容器元件之固體電解質電容器的剖面 圖。 圖2爲，實施例1之電容器元件部份的模式縱向剖面圖 〇 圖3爲，電容器元件層合所得固體電解質電容器之剖 面圖。 [圖號說明] 1 :陽極基體 2:電介質之氧化皮膜層 3 :掩蔽罩 4 :固體電解質 5 :導電體層 6 :導線 7 :導線 8 :環氧樹脂 9 :電容器 -33-[Example 2 (3)] Except that the substrate provided with the solid electrolyte was laminated, the four sheets were laminated in the thickness direction of the laminate, and the carbon paste was adhered to the silver paste to be connected to the cathode lead joint. The other assembly configuration is the same as in the first embodiment. The obtained capacitors were evaluated for the same characteristics as in Example 1, and the results are shown in Table 1. [Example 3] In Example 1, except that pyrrole was substituted for 3,4-ethylenedioxythiophene, at this time -29-1283877 (26), after impregnating the pyrrole solution, it was dried at 3 ° C for 5 minutes, A total of 30 capacitors were completed in the same manner as in Example 1 except that the oxidizing agent solution was immersed at 5 ° C for 10 minutes. In the same manner as in Example 1, the maximum thickness (h!) of the solid electrolyte layer was measured to be 290 μm, the minimum thickness (h2) was 230 μm, and the difference in film thickness (In-lu) was 60 μm. Then, the maximum thickness after compression ( 1^) is 200 μm, the minimum thickness is 180 μm, and the difference in film thickness dhO is 20 μm; after compression, the reduction ratio (Δ Η) of the thickness difference of the solid electrolyte layer is 66.7%. The obtained capacitor element was evaluated for the same characteristics as in Example 1. The results are shown in Table 1. [Comparative Example 1] In Example 1, 30 capacitors were completed in the same manner as in Example 1 except that the capacitor element fabricated without compression molding was used. In the same manner as in Example 1, the maximum thickness (h!) of the solid electrolyte layer was measured to be 260 μm, the minimum thickness was 210 μm, and the difference in film thickness (h^hj was 50 μm). The obtained capacitor element was subjected to the same characteristics as in Example 1. The results are shown in Table 1. [Comparative Example 2] In Example 1, except for the capacitor element which was produced by using the number of times of polymerization which was not subjected to compression 15 times, the same completion as in Example 1 was completed. The same as in Example 1, the maximum thickness (hi) of the solid electrolyte layer was measured as -30 - 1283877 (27) was 180 μm, the minimum thickness (h2) was 120 μm, and the difference in film thickness (dh2) was 6 〇 μ 〇. The obtained capacitor element was subjected to the same special evaluation as in Example 1. The results are shown in Table 1. Table 1 Example Initial characteristic capacity pF Loss factor ESR Leakage current defect rate % (equivalent series resistance) μΑ 1 109 0.7 0.007 0.03 0/30 2(1) 108 0.9 0.008 0.06 0/30 2(2) 109 1.6 0.017 0.03 0/30 2(3) 110 1.8 0.018 0.04 0/30 3 105 1.7 0.014 0.09 1/30 Comparative Example 1 108* 3.6 0.025 0.05 1/30 Comparative Example 2 107 1.9 0.020 0.15 7/30 *Unsealed (when sealed, A part of the components were exposed, and the normal sealing could not be performed. From the results of Examples 1 to 3 and Comparative Examples 1 to 2, it was found that the solid electrolyte having a compression-molded solid electrolyte was flat and the thickness difference (Δ Η) was reduced as much as possible. It is confirmed that it has high capacity, low equivalent series resistance (ESR), and leakage current, and the defect rate is very small, which is extremely advantageous. [Example 4] -31 - 1283877 (28) After the two sheets of the substrate of the conductive polymer composition layer forming the aluminum foil were stacked, the portion forming the conductive polymer composition layer was compression-molded' and Example 1 Similarly, the maximum thickness (hi) of the solid electrolyte layer of the two-layer laminated member of the veneer was 430 μm, the minimum thickness (h2) was 400 μm, and the difference in film thickness (hi-h2) was 30 μm 〇 [Example 5] After the two sheets of the conductive polymer composition layer forming the aluminum foil are stacked, the portion in which the conductive polymer composition layer is formed is compression-molded, and the compression-molded substrate is further stacked, and then compression-molded, and the like. In the same manner as in Example 1, the maximum thickness (In) of the solid electrolyte layer of the four-layer laminated member was 780 μm, the minimum thickness (h2) was 760 μm, and the difference in film thickness (hi-h2) was 20 μm. The solid electrolyte capacitor of the present invention is a substrate on which a solid electrolyte composed of a conductive polymer of an organic polymer is provided on a dielectric film on the surface of a metal porous substrate to which a shutter acts, depending on the thickness of the substrate. A capacitor element having a directionally compressed shape; it has a discrete shape in which a shape can be stably stabilized, and a thin capacitor element can be used to construct a laminated solid electrolyte capacitor having a very low height, a small size and a high capacity, and a solid electrolytic capacitor having no Features such as short defects and stable performance. BRIEF DESCRIPTION OF THE DRAWINGS -32- 1283877 (29) Fig. 1 is a cross-sectional view showing a solid electrolytic capacitor using a capacitor element. Fig. 2 is a schematic longitudinal sectional view showing a portion of a capacitor element of the embodiment 1. Fig. 3 is a cross-sectional view showing a solid electrolytic capacitor obtained by laminating a capacitor element. [Description of the figure] 1 : anode base 2: dielectric oxide layer 3 : mask cover 4 : solid electrolyte 5 : conductor layer 6 : wire 7 : wire 8 : epoxy resin 9 : capacitor -33-